TWI389975B - Thermosetting ethylcarbamate resin composition - Google Patents

Description

Thermosetting urethane resin composition

The present invention relates to a polyurethane containing at least two carboxyl groups per molecule, particularly a polyurethane having one or more carboxyl groups at its molecular terminal, and a thermosetting resin having a thermosetting component. Composition. More specifically, the present invention relates to a thermosetting resin composition which is excellent in adhesion to a substrate, low in flexibility, flexibility, moist heat resistance, solder heat resistance, and tin plating resistance. The thermosetting resin composition of the present invention can be effectively utilized for use in a protective film such as a solder resist or an interlayer insulating film or an electrical insulating material, an IC or a super LSI sealing material, a laminate, or the like.

A thermosetting resin is a material widely used as a tip functional material, and generally has high heat resistance, environmental stability, mechanical properties, electrical properties, etc. as a polymer material having excellent properties, which can be used for plating solder resist or interlayer. Protective film or electrical insulating material such as insulating film, IC or super LSI sealing material, laminate-like use.

However, in the plating resist, there is a problem that the cooling shrinkage due to hardening shrinkage and hardening becomes large.

An epoxy resin-based photoresist composition in which an epoxy resin and a dibasic acid anhydride disclosed in Japanese Patent Publication No. 5-75032 are essential components, for example, in the formed film, It is adjusted so as to impart low bending property, and in the case of flexibility, there is a problem that moisture heat resistance, solder heat resistance, and particularly tin plating resistance are lowered.

Further, a composition for forming a flexible protective film having less bending is disclosed in Japanese Laid-Open Patent Publication No. Hei 11-158252, but the composition is based on a polyfunctional epoxy resin and a specific polyacrylic resin. Since it is an essential component, it is not necessary to regulate the polyacrylic resin from the acid value and the glass transition temperature in order to balance the opposite characteristics (electroplating resistance, etc.), and if low bending property is obtained, The plating resistance is not sufficient.

Invention disclosure

Therefore, the main object of the present invention is to provide a thermosetting property which is excellent in low adhesion and flexibility, and which is excellent in low heat resistance, heat resistance, solder heat resistance, and tin plating resistance, which can solve the above problems. Resin composition.

In order to solve the problem, the present inventors have found that a polyurethane containing a carboxyl group having two or more carboxyl groups per molecule (A) is particularly a polyamine group having one or more carboxyl groups at a molecular terminal thereof. The thermosetting resin composition of ethyl formate and thermosetting component (B) has good adhesion to the substrate, low bendability, flexibility, moisture resistance, solder heat resistance, and tin plating resistance. It is excellent and the problem can be solved, and thus the present invention has been completed.

In other words, the present invention relates to a thermosetting resin composition represented by the following 1 to 25, wherein the cured product is a solder resist and a protective film, and a printed wiring board covered with the cured product.

A thermosetting resin composition comprising: a polyurethane having a carboxyl group of two or more carboxyl groups (A) and a thermosetting component (B).

2. The thermosetting resin composition according to claim 1, wherein the polyurethane (A) is a polyurethane having one or more carboxyl groups at a molecular terminal.

3. The thermosetting resin composition according to claim 1, wherein the polyurethane (A) has two or more carboxyl groups per molecule and has a polymer polyol (b). The urethane bond of the urethane bond formed by the reaction with the polyisocyanate (c).

4. The thermosetting resin composition according to claim 2, wherein the polyurethane (A) is a functional group having an addition reaction or a condensation reaction with an isocyanate group in the molecule. Polyurethane (A) formed by a terminal sealing reaction of a monocarboxylic acid compound (a) having both carboxyl groups, which has one or more polyaminocarboxylic acids having two or more carboxyl groups per molecule at the molecular terminal Ethyl ester (A).

5. The thermosetting resin composition according to claim 1, wherein the polyurethane (A) has an average number average molecular weight of 500 to 100,000 and an acid value of 5 to 150 mgKOH/g.

6. The thermosetting resin composition according to claim 4, wherein the monocarboxylic acid compound (a) having both a functional group and a carboxyl group obtained by an addition reaction or a condensation reaction with an isocyanate group in the molecule is a monocarboxylic acid compound (a). At least one selected from the group consisting of a monocarboxylic acid compound having a hydroxyl group, a monocarboxylic acid compound having an amino group, and a monocarboxylic acid compound having a thiol group.

7. The thermosetting resin composition according to claim 4, wherein the monocarboxylic acid compound (a) is a monohydroxycarboxylic acid.

8. The thermosetting resin composition according to claim 3, wherein the polymer polyol (b) is selected from the group consisting of polycarbonate-based polyalcohols, polyether-based polyalcohols, polyester-based polyalcohols, and polyolefins. At least one of a group of a polyalcohol and an acrylic polyalcohol.

9. The thermosetting resin composition according to claim 3, wherein the polymer polyol (b) is a polycarbonate diol.

10. The thermosetting resin composition according to claim 9, wherein the polycarbonate diol has a number average molecular weight of 200 to 5,000.

11. The thermosetting resin composition according to claim 9 or 10, wherein the polycarbonate diol is selected from the group consisting of one or more selected from the group consisting of linear aliphatic diols. A repeating unit of polycarbonate diol, a polycarbonate diol containing one or more repeating units derived from an alicyclic diol, and a polycarbonate of a repeating unit derived from the diol of the two At least one of a group of diols.

12. The thermosetting resin composition according to claim 11, wherein the polycarbonate diol has a constituent unit containing a poly unit derived from a repeating unit of a linear aliphatic diol and an alicyclic diol. The carbonate diol has a number average molecular weight of 400 to 2,000, and the mass ratio of the linear aliphatic diol to the alicyclic diol is 3:7 to 7:3.

The thermosetting resin composition according to claim 3, wherein the polyisocyanate (c) is an alicyclic diisocyanate derived from an alicyclic diamine.

14. The thermosetting resin composition according to claim 3, wherein the polyurethane (A) is a polyalcohol having a carboxyl group in addition to the polymer polyol (b) and the polyisocyanate (c). (d) The reaction is obtained.

15. The thermosetting resin composition according to claim 14, wherein the polyalcohol (d) having a carboxyl group is a dihydroxy aliphatic carboxylic acid.

The thermosetting resin composition according to claim 1, wherein the thermosetting component (B) is an epoxy resin.

17. The thermosetting resin composition according to claim 16, wherein the epoxy resin is selected from the group consisting of bisphenol S type epoxy resin, digoxypropyl phthalate resin, and heterocyclic epoxy resin. At least one of a group of a resin, a bis xylenol type epoxy resin, a bisphenol type epoxy resin, and a tetra-glycidyl dimethyl phenol ethane resin.

The thermosetting resin composition according to claim 16 or 17, wherein the polyaminourethane (A) having one or more molecular groups and two or more carboxyl groups per molecule is used. The carboxyl equivalent weight is a ratio of the epoxy equivalent of the epoxy resin of the thermosetting component (B) of 1.0 to 3.0.

19. The thermosetting resin composition according to claim 1, further comprising a curing agent.

20. The thermosetting resin composition according to claim 19, wherein the hardener is selected from the group consisting of an amine, a quaternary ammonium salt, an acid anhydride, a polyamine, a nitrogen-containing heterocyclic compound, and an organometallic compound. At least one of them.

21. The thermosetting resin composition according to claim 1, further comprising an organic solvent.

A cured product obtained by curing a thermosetting resin composition according to any one of claims 1 to 21 of the invention.

A solder resist which is characterized by being a cured product as described in claim 22 of the patent application.

A protective film comprising the cured product according to claim 22 of the patent application.

A printed wiring board characterized by being partially or fully covered with a cured material as described in claim 22 of the patent application.

The thermosetting resin composition containing the ethyl urethane bond (A) having a urethane bond and the thermosetting component (B) according to the present invention has adhesion to a substrate, and has low flexibility. Excellent in flexibility, heat and humidity resistance, solder heat resistance, and tin plating resistance. It is used in protective films such as plating resists or interlayer insulating films, electrical insulating materials, ICs, super LSI sealing materials, laminates, etc. Use can be used properly. In the conventional soldering resist, since the cooling shrinkage after hardening shrinkage and hardening is large, bending occurs and the productivity is lowered. However, according to the thermosetting resin composition of the present invention, low bending property can be achieved at the same time. Flexibility is a trade-off relationship between solder heat resistance, damp heat resistance, and electroplating resistance, and includes a polyurethane having one or more molecular terminals and two or more carboxyl groups per molecule. (A) and the thermosetting resin composition of the thermosetting component (B) are particularly excellent in tin plating resistance, excellent in plating resist, or in which the protective film is excellent in productivity at low cost.

The best form of implementing the invention

The invention is described in detail below.

The polyurethane (A) has two or more carboxyl groups per molecule and has a urethane bond formed by the reaction of the polymer polyol (b) with the polyisocyanate (c). The polyurethane (A) is formed, for example, by a terminal sealing reaction of a monocarboxylic acid compound (a) in which a functional group and a carboxyl group obtained by an addition reaction or a condensation reaction with an isocyanate group are used in a molecule, There are at least one molecular terminal at the molecular terminal and two or more carboxyl groups per molecule. In the case of the terminal sealant, it can be reacted with the monocarboxylic acid compound (a), and in order to adjust the acid value, the polyalcohol (d) having a carboxyl group may be further added to the polymer polyol (b) and the polyisocyanate (c). . Monohydroxy compounds can also be used in the case of terminal sealants.

The monocarboxylic acid compound (a) is used for the purpose of allowing a carboxyl group to be present at the terminal of the polyurethane (A), and is a terminal sealant of the polyurethane (A), if it is in the molecule. A monocarboxylic acid compound having both a functional group and a carboxyl group obtained by reacting with an isocyanate is preferred. Specific examples of the monocarboxylic acid compound (a) include a functional group obtained by an addition reaction or a condensation reaction with an isocyanate group, for example, a monocarboxylic acid having a hydroxyl group, an amino group, or a mercaptan, for example, a monohydroxycarboxylic acid (a1) a monocarboxylic acid (a2) having an amino group, or a monocarboxylic acid (a3) having a thiol group, or the like. Specific examples of the monohydroxycarboxylic acid (a1) include glycolic acid, lactic acid, hydroxytrimethylacetic acid, malic acid, and citric acid. Specific examples of the monocarboxylic acid (a2) having an amino group include glycine and the like. Specific examples of the monocarboxylic acid (a3) having a thiol group include thioglycolic acid and the like.

The use of the monocarboxylic acid (a) in both the functional group and the carboxyl group which can react with the isocyanate group in the molecule enables the ethyl urethane (A) to exist at the terminal carboxyl group of the molecule and is in close contact with the substrate. It is excellent in properties, low in flexibility, and flexibility, and is excellent in moisture heat resistance, solder heat resistance, and plating resistance. In particular, it is possible to obtain a thermosetting resin composition excellent in tin plating resistance.

The polymer polyol (b) may, for example, be a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, or an acrylic polyol. The polycarbonate-based polyol is preferably a polycarbonate diol. In the polycarbonate diol, the polycarbonate diol (b1) containing one or more kinds of repeating units derived from a linear aliphatic diol as a constituent unit contains one or more kinds from the alicyclic formula. The repeating unit of the diol is a polycarbonate diol (b2) as a constituent unit, or a polycarbonate diol (b3) containing a repeating unit derived from the diols as the constituent unit.

Specific examples of the polycarbonate diol (b1) containing a repeating unit derived from a linear aliphatic diol as a constituent unit may, for example, be a polycarbonate diol derived from 1,6-hexanediol. a polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol, a polycarbonate diol derived from 1,4-butanediol and 1,6-hexanediol, A polycarbonate diol derived from 3-methyl-1,5-pentanediol and 1,6-hexanediol.

Specific examples of the polycarbonate diol (b2) containing a repeating unit derived from an alicyclic diol as a constituent unit may, for example, be a polycarbonate diol derived from 1,4-cyclohexanedimethanol.

Specific examples of the polycarbonate diol (b3) containing a repeating unit derived from a diol of a linear aliphatic diol and an alicyclic diol as a constituent unit may, for example, be 1,6- A polycarbonate diol derived from hexanediol and 1,4-cyclohexanedimethanol.

The polycarbonate diol containing a repeating unit derived from a linear aliphatic diol as a constituent unit tends to have low flexibility or flexibility. In addition, the polycarbonate diol containing a repeating unit derived from an alicyclic diol as a constituent unit tends to have high crystallinity and tin plating resistance, and is excellent in solder heat resistance. From the above viewpoints, the polycarbonate diols may be used in combination of two or more kinds, or a repeating unit containing a diol derived from both a linear aliphatic diol and an alicyclic diol. A unit of polycarbonate diol can be used. In order to achieve low bendability or flexibility, and to exhibit uniformity in solder heat resistance and tin plating resistance, the copolymerization ratio of the linear aliphatic diol to the alicyclic diol is a mass ratio of 3: The use of 7 to 7:3 polycarbonate diol is appropriate.

The polycarbonate diol preferably has a number average molecular weight of 200 to 5,000, but the polycarbonate diol as a constituent unit contains a repeating unit derived from a linear aliphatic diol and an alicyclic diol, and a linear fat The copolymerization ratio of the diol and the alicyclic diol is preferably from 3 to 7:7 by mass ratio, and the number average molecular weight is preferably from 400 to 2,000.

Specific examples of the polyisocyanate (c) include, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, hexylene diisocyanate, diphenylmethylene di Isocyanate, (o-, m- or p-)-xylene diisocyanate, (o-, m- or p-)-hydroxylene diisocyanate, methylene bis(cyclohexyl isocyanate), trimethyl hexylene diisocyanate, cyclohexane a diisocyanate such as 1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate or 1,5-naphthalene diisocyanate. These polyisocyanates may be used alone or in combination of two or more. The alicyclic diisocyanate derived from the alicyclic diamine, in particular, isophorone diisocyanate or (o-, m- or p-)-hydroxylene diisocyanate is preferred. In the case of using such a diisocyanate, a cured product excellent in tin plating resistance can be obtained.

In the case of the polyol (d) having a carboxyl group, it is particularly preferable to use a dihydroxyaliphatic carboxylic acid having a carboxyl group. The dihydroxy compound may, for example, be dimethylolpropionic acid or dimethylolbutanoic acid. By using a dihydroxy aliphatic carboxylic acid having a carboxyl group, a carboxyl group can be easily present in the urethane resin.

In terms of the monohydroxy compound, a compound having a monohydroxy group in the molecule may be preferred because it can be an end sealer of the ethyl urethane (A), and an aliphatic alcohol, monohydroxy mono(methyl) may be exemplified. Acrylate compound, etc. Examples of the aliphatic alcohols include methanol, ethanol, propanol, isobutanol, and the like, and examples of the monohydroxy mono(meth)acrylate compound include 2-hydroxyethyl acrylate.

The number average molecular weight of the urethane resin (A) is preferably from 500 to 100,000, more preferably from 8,000 to 30,000. Here, the number average molecular weight is a polystyrene-converted value measured by gel permeation chromatography. When the number average molecular weight of the urethane resin (A) is less than 500, the elongation of the cured film may be impaired, flexibility, and strength may be obtained, and when it exceeds 100,000, the resin may become hard and the flexibility may be lowered. .

The acid value of the urethane resin (A) is preferably from 5 to 150 mgKOH/g, more preferably from 30 to 120 mgKOH/g. When the acid value is less than 5 mgKOH/g and the reactivity with the curable component is lowered, the heat resistance is impaired. When the amount is more than 50 mgKOH/g, the alkali resistance of the cured film and the characteristics of the photoresist such as electrical characteristics may be lowered. Further, the acid value of the resin is a value measured in accordance with JIS K5407.

As the thermosetting component (B), an epoxy resin which reacts with the polyurethane of the component (A) can be used. Specific examples of the epoxy resin, such as bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin , phenol novolac type epoxy resin, cresol novolak type epoxy resin, N-epoxypropyl type epoxy resin, bisphenol A novolak type epoxy resin, clamp type epoxy resin, Ethylene Aldehyde type epoxy resin, amino group containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenolic type epoxy resin, polyfluorene modified epoxy resin, ε-caprolactone modification An epoxy compound having two or more epoxy groups in one molecule such as an epoxy resin. Further, in order to impart flame retardancy, an atom such as chlorine, bromine or the like such as a halogen or phosphorus may be introduced into the structure. Further, a bisphenol S type epoxy resin, a digoxypropyl phthalate resin, a heterocyclic epoxy resin, a bisxylenol type epoxy resin, a bisphenol type epoxy resin, and a tetracyclic ring can also be used. Oxypropyl dimethyl phenol ethane resin and the like.

In the thermosetting resin composition of the present invention, the thermosetting component (B) may be used singly or in combination of two or more kinds. The amount of the epoxy group equivalent of the epoxy group of the thermosetting component (B) to the carboxyl group equivalent of the carboxyl group of the (A) component is 1.0 to 3.0. Expected. When the thickness is less than 1.0, the electrical insulating property of the cured film of the thermosetting resin composition may be insufficient. When the thickness exceeds 3.0, the amount of shrinkage of the cured film increases, and it is used as a flexible printed wiring board ( In the case where the insulating protective film of FPC) is used, there is a tendency that the low bending property is deteriorated.

The curing agent used in the present invention is used to promote the thermosetting reaction, and is used to further improve the properties of adhesion, chemical resistance, heat resistance and the like. Specific examples of such a curing agent include an imidazole derivative (for example, manufactured by Shikoku Kasei Kogyo Co., Ltd., 2MZ, 2E4MZ, C _{1 1} Z, C _{1 7} Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN) , C _{1 1} Z-CN, 2PZ-CN, 2PHZ-CN, 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C _{1 1} Z-AZINE, 2MA-OK, 2P4MHZ, 2PHZ , 2P4BHZ, etc.; guanine guanamine, guanine guanamine and other guanamine amines; diaminodiphenylmethane, phenyldiamine, m-xylenediamine, diaminodiphenyl Polyamines such as hydrazine, dicyanodiamine, urea, urea derivatives, melamine, polybasic hydrazines, etc.; organic acid salts and/or epoxy adducts; Boron amine complex; ethyldiamine-s-three , 2,4-diamino-s-three , 2,4-diamino-6-dimethylphenyl-s-three Three Derivatives; trimethylamine, triethanolamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholinyl, hexa(N-methyl)melamine , 2,4,6-tris(dimethylaminophenol), amines such as guanidine, m-aminophenol, polyvinylphenol, polyvinylphenol bromide, phenol novolac, alkyl Polyphenols such as phenol novolac; tributylphosphine, triphenylphosphine, organic phosphines such as tris-cyanoethylphosphine; tri-n-butyl bromide (2,5-dihydroxyphenyl)鏻, a sulfonium salt such as hexadecylphosphonium chloride; a quaternary ammonium salt such as benzyltrimethylammonium chloride or phenyltributylammonium chloride; the polybasic acid anhydride; Phenyl iodide tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyranium hexafluorophosphate, manufactured by CIBA-Geigy, Irgacure- 261, photo-cationic polymerization catalyst of Optoma SP-170, manufactured by Asahi Chemical Co., Ltd.; styrene-maleic anhydride resin; molar reaction of phenyl isocyanate with dimethylamine or toluene diisocyanate, Ketone II The organic diisocyanate and the like known polyisocyanates of dimethylamine and equimolar reaction product of the conventional curing agents or curing promoting agents.

These hardeners may be used singly or in combination of two or more. The use of the curing agent is not essential, and in particular, in the case where it is desired to promote hardening, it is preferably used in an amount of 25 parts by mass based on 100 parts by mass of the thermosetting component (B). When the amount exceeds 25 parts by mass, the sublimation component from the hardened material may become unsatisfactory.

In the thermosetting resin composition of the present invention, the polyurethane (A) and the thermosetting component (B) are a mixer, for example, a disperser, a kneader, a three-roll mill, a ball mill, or the like. , obtained by dissolving or dispersing. In this case, an inert solvent can be used with respect to the epoxy group and the carboxyl group. An organic solvent is preferred for such an inert solvent.

The organic solvent can be used because the above-mentioned polyurethane (A) and the thermosetting component (B) can be easily dissolved or dispersed, or adjusted to a viscosity suitable for a coating film. In terms of organic solvents, for example, toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, carbitol acetate , propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, methyl methoxypropionate, methoxypropionic acid Ethyl ester, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexanone, N , N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, dimethyl hydrazine, chloroform and methylene chloride.

Further, the thermosetting resin composition of the present invention can be blended with various additives such as barium sulfate, talc, calcium carbonate, alumina, glass powder, quartz powder, cerium oxide, etc., inorganic filler, glass fiber, carbon fiber. , fiber reinforced materials such as boron nitride fibers, titanium oxide, zinc oxide, carbon black, iron black, organic pigments, colorants such as organic dyes, hindered phenol compounds, phosphorus compounds, hindered amine compounds, etc. A benzotriazole-based compound, a absorbing agent such as a benzodiphenyl ketone-based compound, or the like.

Moreover, a mixed viscosity adjuster, a flame retardant, an antibacterial agent, an antifungal agent, an anti-aging agent, an antistatic agent, a plasticizer, a slip agent, a foaming agent, etc. may be added for the purpose of use.

Example

The invention is further illustrated by the following examples, but the invention is not limited by the examples.

Synthesis Example 1: Synthesis of Polyurethane (PU-1) In a reaction vessel equipped with a stirring device, a thermometer, and a capacitor, a mixture of 1,5-pentanediol and 1,6-hexanediol was charged. Carbonate diol (PCDL800, number average molecular weight 800), 2400 g (3 mol), dihydroxy compound with carboxyl group, 402 g (3 mol) of dimethylolpropionic acid, polyisocyanate input Isophorone diisocyanate 1554 g (7 mol) and a monohydroxy compound were charged with 2-hydroxyethyl acrylate, 238 g (2.05 mol). With stirring and heated to 60 deg.] C to be stopped, at the time it begins to decrease the temperature inside the reaction vessel was again heated stirring was continued at 80 ℃, an infrared absorption spectrum confirmed that the absorption spectrum of the isocyanate group of (2280 cm ^{- 1)} disappears to complete the reaction. The carbitol acetate was added in such a manner that the solid content became 50% by mass to obtain a polyurethane urethane (PU-1) containing a liquid viscous liquid of a diluent. The number average molecular weight of the obtained polyurethane was 22,000 (average molecular weight was used, and gel carrier liquid chromatography (GPC-1 manufactured by GPC Showa Denko Co., Ltd.) was used to obtain the value converted into polystyrene. The acid value of the solid component was 46 mgKOH/g.

Synthesis Example 2: Synthesis of urethane resin (PU-2) Polycarbonate diol was a polycarbonate diol derived from 1,6-hexanediol and 1,4-cyclohexanedimethanol ( Ubiquita Co., Ltd., UM-CARB90, a number average molecular weight of 900, and a copolymerization ratio of the above two kinds of diols was synthesized in the same manner as in Synthesis Example 1 except that the mass ratio was 1:1) 2700 g, and a diluent was obtained. Polyurethane PU-2 of liquid viscous liquid. The obtained polyethyl urethane had a number average molecular weight of 24,000 and a solid component acid value of 57 mgKOH/g.

Comparative Example 1: A styrene-acrylic resin manufactured by Johnson Polymer Co., Ltd.; JONCRYL 586 (molecular weight 4600, solid component acid value 108 mgKOH/g) was used as a carboxyl group-containing resin.

Comparative Example 2: A propylene-based copolymer resin manufactured by Daicel Chemical Industry Co., Ltd.; cyclomer PACA320 (having a molecular weight of 20,000 and a solid component acid value of 130 mgKOH/g) was used as a carboxyl group-containing resin.

Examples 1 to 3 and Comparative Examples 1 and 2: The curable resin composition was prepared by mixing (23 ° C) in three rolls with the respective components and mixing ratios shown in Table 1. The obtained thermosetting composition was coated on a substrate with a bar coater to a film thickness of about 25 μm. Each of the coating film substrates was preliminarily dried at 80 ° C for 15 minutes, and then thermally cured at 150 ° C × 60 minutes.

The performance in each case was evaluated by the following method. The results are shown in Table 1.

Performance evaluation

(1) Flexibility A thermosetting resin composition was coated on a polyimide film (kapton 100H; manufactured by Toray Dupont Co., Ltd., thickness: 25 μm), and heat-hardened, and then a circular cutter at 50 mm Φ (circle cutter) ) cutting. The person who is cut into a circular shape exhibits a deformation opposite to the convex or concave shape near the center. After 1 h, it was allowed to stand in a state of being convex below, and the maximum and minimum values of the bending height from the horizontal plane were measured and averaged. The symbol indicates the direction of the bending, and when it is left in a state of being convex, the case where the cured film is on the upper side with respect to the polyimide film is +, and the case where the cured film is on the lower side is -.

(2) Flexibility A sample which was subjected to thermal curing was cut into 15 × 70 mm on a polyimide film (kapton 100H; manufactured by Toray Dupont Co., Ltd., thickness: 25 μm), and bent at 180 degrees to become light. The resistance surface faces outward, and the bending portion is subjected to a force of 0.35 kN for 1 second. When observed under a microscope, the number of cracks was observed to be measured by flexibility. In addition, the evaluation was carried out up to 10 times.

(3) Solder heat resistance A part of a rigid copper substrate was masked with a kapton polyimide tape (manufactured by Toray Dupont Co., Ltd.), and the mask surface and the non-mask surface were coated. Membrane, a hardened coating film is obtained. Next, the kapton polyimide tape was peeled off, and the rosin-based solder was applied, and immersed in a solder bath at 260 ° C for 10 sec. The interface between the photoresist film and the tape peeling portion was visually observed to evaluate the number of times of immersion until the change in film peeling or the like occurred. In addition, the evaluation was performed up to three times.

(4) Adhesion

A hardened coating film was applied to a copper substrate, a polyimide film (kapton 300H; manufactured by Toray Dupont Co., Ltd., thickness: 100 μm), and evaluated in accordance with JIS K5600. In addition, the tape for peeling is made by Nitto.

○: The number of checkerboard eyes is completely residual

△: The number of checkerboard eyes is less than 50 and less than 100 remains.

×: The number of checkerboard eyes is less than 50

(5) PCT (pressure cooker test: heat and humidity resistance test)

A hardened coating film was obtained on a flexible copper substrate (manufactured by Ube Industries, Ltd.: Upicel NSE3150) at a temperature of 121 ° C and a relative humidity of 100% RH. After standing in a humidity machine for 120 hours, it was evaluated on the following basis.

○: no swelling, peeling, discoloration in the cured coating film

△: There are some expansion, peeling, and discoloration in the hardened coating film.

×: expansion, peeling, discoloration in the cured coating film

(6) Tin resistance

A hardened coating film was obtained on a flexible copper substrate (made by Ube Industries, Ltd.: Upicel N SE3150), and it was immersed in a plating bath of 70 ° C at a plating bath (manufactured by Rohm & Haas Co., Ltd.: TINPOSITLT-34) for 3 minutes, and then washed. (washing) (70 ° C, 3 points), visual evaluation was performed on the following basis.

○: There is no expansion in the cured coating film, peeling, discoloration Δ: There is a certain expansion in the cured coating film, peeling, discoloration ×: swelling, peeling, discoloration in the cured coating film

Synthesis Example 3: Synthesis of urethane resin "PU-3" In a reaction vessel equipped with a dropping funnel, a stirring device, a thermometer, and a capacitor, 1,6-hexanediol and 1,4-cyclohexanedimethanol were used. The polycarbonate diol (manufactured by Ube Industries, Ltd., UM-CARB90, number average molecular weight 900, copolymerization ratio of the above two kinds of diols in a mass ratio of 1:1) was put into 1,800 g (=2 mol), and The dihydroxy compound of the carboxyl group was charged with 402 g (=3 mol) of dimethylolpropionic acid and 1,554 g (=7 mol) of isophorone diisocyanate. The mixture was stopped while being heated to 60 ° C while stirring, and heated again when the temperature in the reaction vessel began to decrease, and stirring was continued at 80 ° C for 2 hours. The monocarboxylic acid compound of the terminal sealant was charged with 153 g (= 2 mol) of glycolic acid as a dropping funnel, and stirring was continued for 2 hours at the same temperature. In the infrared absorption spectrum confirmed that the absorption spectrum of the isocyanate group (2280 cm ^{- 1)} have disappeared to complete the reaction. The carbitol acetate was added to have a solid content of 50% by mass, and a urethane resin PU-3 containing a liquid viscous liquid of a diluent was obtained. The number average molecular weight of the obtained polyurethane was 3,900 (the average molecular weight was determined by using gel carrier liquid chromatography (GPC-1, manufactured by GPC Showa Denko Co., Ltd.) in terms of polystyrene. The acid value of the solid component is 87 mgKOH/g.

Synthesis Example 4: Synthesis of urethane resin "PU-4" The same procedure as in Synthesis Example 3 except that 237 g (=2 mol) of hydroxytrimethylacetic acid was used as the monocarboxylic acid compound of the terminal sealant. The synthesis was carried out to obtain a urethane resin PU-4 containing a liquid viscous liquid of a diluent. The obtained polyurethane had a number average molecular weight of 4,000 and a solid content of 85 mgKOH/g.

Synthesis Example 5: Synthesis of urethane resin [PU-5" The same procedure as in Synthesis Example 3 was carried out except that the monohydroxyl compound of the terminal sealant was 235 g (=2 mol) using 2-hydroxyethyl acrylate. The synthesis was carried out to obtain a urethane resin PU-5 containing a liquid viscous liquid of a diluent. The obtained polyurethane had a number average molecular weight of 4,000 and a solid content of an acid value of 57 mgKOH/g.

Synthesis Example 6: Synthesis of urethane resin "PU-6" Synthesis was carried out in the same manner as in Synthesis Example 3 except that the monohydroxy compound of the terminal sealant was 148 g (=2 mol) using isobutanol. A urethane resin PU-6 which is a liquid viscous liquid containing a diluent is obtained. The obtained polyurethane had a number average molecular weight of 4,000 and a solid content of 58 mgKOH/g.

Comparison of Examples 4 and 5 with Examples 6 and 7: Each of the components and the compounding ratio shown in Table 2 were mixed by a triple roll (23 ° C) to prepare a thermosetting resin composition. The obtained thermosetting resin composition was coated on a substrate with a bar coater to have a film thickness of about 25 μm. Each of the coated substrates was subjected to solvent pre-drying at 80 ° C for 15 minutes, and then thermally cured at 150 ° C × 60 minutes. The results of the performance evaluation by the method in each of the examples are shown in Table 2 together with the comparative examples 1, 2.

Industrial availability

As described above, the thermosetting resin composition containing the polyurethane (A) and the thermosetting component (B) according to the present invention has adhesiveness to a substrate, low flexibility, flexibility, and moist heat resistance. It is excellent in solder heat resistance and tin plating resistance, and can be suitably used for electrical insulating materials such as solder resists or interlayer insulating films, ICs, super LSI sealing materials, laminates, and the like.

Claims (21)

A thermosetting resin composition comprising: a polyurethane having a carboxyl group of two or more carboxyl groups (A) and a thermosetting component (B), and the polyurethane (A) a urethane bond formed by the reaction of a polymer polyol (b) with a polyisocyanate (c), wherein the polymer polyol (b) is selected from the group consisting of one or two The above polycarbonate diol derived from a repeating unit of a linear aliphatic diol, one or two or more kinds of polycarbonate diols derived from repeating units of an alicyclic diol, and from both At least one of a group of polycarbonate diols in which the diol is repeated. The thermosetting resin composition of claim 1, wherein the polyurethane (A) is a polyurethane having one or more carboxyl groups at a molecular terminal. The thermosetting resin composition of claim 2, wherein the polyurethane (A) is a functional group and a carboxyl group obtained by an addition reaction or a condensation reaction with an isocyanate group in a molecule. The polyurethane (A) formed by the terminal sealing reaction of the monocarboxylic acid compound (a) is a polyurethane having one or more terminal groups at the molecular end and having two or more carboxyl groups per molecule ( A). The thermosetting resin composition of claim 1, wherein the polyurethane (A) has an average molecular weight of 500 to 100,000 and an acid value of 5 to 150 mgKOH/g. The thermosetting resin composition of claim 3, wherein the monocarboxylic acid compound (a) having both a functional group and a carboxyl group obtained by an addition reaction or a condensation reaction with an isocyanate group in the molecule is selected from the group consisting of At least one of a group of a monocarboxylic acid compound having a hydroxyl group, a monocarboxylic acid compound having an amino group, and a monocarboxylic acid compound having a thiol group. The thermosetting resin composition of claim 5, wherein the monocarboxylic acid compound (a) is a monohydroxycarboxylic acid. The thermosetting resin composition of claim 1, wherein the polycarbonate diol has a number average molecular weight of 200 to 5,000. The thermosetting resin composition of claim 1, wherein the polycarbonate diol has a constituent unit containing a polycarbonate unit derived from a repeating unit of a linear aliphatic diol and an alicyclic diol. The alcohol has a number average molecular weight of 400 to 2,000, and the mass ratio of the linear aliphatic diol to the alicyclic diol is 3:7 to 7:3. The thermosetting resin composition of claim 1, wherein the polyisocyanate (c) is an alicyclic diisocyanate derived from an alicyclic diamine. The thermosetting resin composition of claim 1, wherein the polyurethane (A) is a polyalcohol having a carboxyl group (d) in addition to the polymer polyol (b) and the polyisocyanate (c). The reaction is obtained. The thermosetting resin composition of claim 10, wherein the polyalcohol (d) having a carboxyl group is a dihydroxy aliphatic carboxylic acid. For example, the thermosetting resin composition of claim 1 of the patent scope, Among them, the thermosetting component (B) is an epoxy resin. The thermosetting resin composition of claim 12, wherein the epoxy resin is selected from the group consisting of bisphenol S type epoxy resin, diepoxypropyl phthalate resin, heterocyclic epoxy resin, and double At least one of a group consisting of a xylenol type epoxy resin, a bisphenol type epoxy resin, and a tetra-glycidyl dimethyl phenol ethane resin. The thermosetting resin composition according to claim 12 or 13, wherein the carboxyl group equivalent of the polyurethane (A) having one or more and having two or more carboxyl groups per molecule is used. The ratio of the epoxy equivalent of the epoxy resin which is the thermosetting component (B) is from 1.0 to 3.0. The thermosetting resin composition of claim 1, which further contains a curing agent. The thermosetting resin composition of claim 15, wherein the curing agent is at least one selected from the group consisting of an amine, a quaternary ammonium salt, an acid anhydride, a polyamine, a nitrogen-containing heterocyclic compound, and an organometallic compound. . The thermosetting resin composition of claim 1, which further contains an organic solvent. A cured product obtained by curing a thermosetting resin composition according to any one of claims 1 to 17 of the patent application. A plated solder resist characterized by being formed as a cured product of claim 18 of the patent application. A protective film characterized by being formed as a cured product of claim 18 of the patent application. A printed wiring board characterized by being partially or fully covered with a cured material as claimed in claim 18 of the patent application.